Conversion of carbonaceous materials



Junev17, 1952 E. w. RIBLETT CONVERSION A'OF' CARBONACEOUS MATERIALS Filed Aug. 9, 194'?l mm. lll

Vpatented June 17, 1952 UNITED 'STATES Parnu-T vorm-es CONVERSION 0F cARBeNAeEoUs MATERIALS e Een Ritiert'grensay, N g.;ssgor'ttnyam; A 'carbonltjesnearcm Inc., New York, N.' Y., 'a core porationof New Jersey Appiieatien 'Aug-ust 9, 1947,- sereiNa'rsme-s's solenne. (o1. 19t-Lee) This invention relates to the earponiia'tionand gasification ofsolid carbon'aceous rr'ifatriahcomb ined with the cracking of oil or other hydrocarbon material. Y Y. e e

y It is an object of this invention to process solid carbonaceous material such as coal, lignite, Yeil shale, andthe like,,andconcurrentlylefiect the crackingof hydrocarbons ina novel manner wherein substantially all the fuelv requirements for both operations are taken from the solid carbonaceous material. e y

.A further Object of this invention' 1S the. 1211?- vision of va, novel combined process for treating solid. carbonaceous Vmaterials and eiecting the ,cracking of hydrocarbons, for example, gasoil hydrocarbons wherein Athe processing of .fresh material, thegresultant coke,and the oil are handledA in a s'implied and ecient manner.

Other objects of the invention will appear yfrom thefollowing description andclaimsetaken in connection with the attached ydrawingWhereina preferredembodiment of a process according to the present invention is shown in diagram- Ymatic form. Y, A A :Inuits broader aspect;v the present invention involves the combined carbonization and gasiiication of solid carbonaceousmaterialjsuch as coal, lignite, etc., with the productionof coke, the coke being exothermically reacted, for instance, With oxygen or with hydrogen at elevated pressure to supply ;the heat requirements for coking fresh` material and for cracking hydrocarbons derived from petroleum, coal or any vother source. In the cra-cking of r the hydrocarbon by contact with the heated cokeirom the gasication step, all the vaporized products thereof are conserved and the nonrecoverable solid products become combined with the coke and are thereafter processed therewith. A feature of the invention is the use 4of hot coke from' Vthe gasifier as contact agent 'for crachinghydro- 'carbone The coke or solid residue l'drawn from the gasier has appreciable vcatalytic effecten the cracking reaction.

In. ai specific embodiment, the invention .cone 'A'tmplatesthe carbonization-of carbonaceou's material, gasification .of coke, cracking 1o'foil ina iiuidized system, whereby. the necessary ow offbeat from the gasifier to'theearb'onizer and the cracking unit is materially facilitatedvand improved.

The invention also involves the processing of the coke and oil ina manner such that the coke andthe solid carbon'alcveous5y oducts'ffrorn Vthe "2 oi desired ga'smvmi'xture such vas synthesis lgas. consisting essentially oflcarbonfxnonoiiide and hydrogen, for the subsequent synthesis of 'hydroca rbons', oxygenated compounds and the like.

Referring .i0 .the @washed @ravine readers 'u' '2 and "3 are O f typesfwherem the material therein can `be luidized, the solid'material being preferably charged thereto. as particles of.: siaes less thanwlild mesh and usnally at leastfper cent thereof being smaller than "290 mesh, and

la udizine eas passed. upwardly threthrwsh at av velocity of about 9,5 to 2.5 feet persecond.

Under gsfuch conditions the solids are highly agitated and the mass behaves in @manner .analogous to a boiling mass ofliquidg The,heatexchange between the particles and the fluidizing medium is highly eiiient, .e The boiling oebullient action also enables the ready separation of -gaseous products from the mass, `any such products generated in the mass operating to further the fluidization. v

Freshv solid carbonaceous material, coal being discussed' herein by way of example, is fedfin vparticle form from a hopper I4 into a line I5 vinto admixture with g hot coke -at Va temperature (1fabout 2ooo F. fed-'t0 une lsfrem e liners.. .The conveyance ofthe solids is eiectedbysuspension in a gas fedinto line l5; lfor -instance,

tail gas from a Fischer-type synthesisoperation may be utilized. Also, this gas may be taken from the gas produced in reactor il 4by passing part of the product gasin line 3l through line 3 2 and pump Ainto line 1.5; Itis desirable -that the gas be relatively-inert as regards'Y the solids chargedto reactor l2 to the extent that littleor no oxidation takes place therein.

The fresh Ycoalancl the hot coke are ui'dized .together in reactor n I2, the temperature Iof fthe mass beingabove about "10'00" landf'suita'bly in the 'apprximate'rahgeof 1413!);1'600D F. "'At Y this temperature, the volatile components ofthe coal' 'are' vaporiaed and removed at the t'p of' the i4reactor with the iiuidizing medium throughfaline fs'veparatorfg to collectfandfreturh V'the -solio'lsto thev reactor vas shown. The jgas mixture, las freturned to reactor Il through line 2l'. Product coke may be taken oif via line 22. Coke maiT also be discharged from the reactor l2 through line 24 into line 23, where it is admixed with vaporized hydrocarbon oil. Some of the coke may be returned to reactor il by a line 2| and some removed as product coke at 22.

The hydrocarbon oil, for example a gas oil fraction from refinery operations with an atmospheric boiling range of 525 to 760 F., is charged through line 23, hot coke being fed therein from line Ilia or from line 24 or from both of them simultaneously. Preferably, the oil is preheated to a temperature of 600 to 800 F. The oil, if not supplied in vapor form, may be vaporized in line 23 by the admixture therewith of hot coke from line 18a and/or line 24. The coke is iiuidized in reactor I3 by the oil vapors, the temperature of the reactor being about 900 to 1200 F. The oil is cracked by reason of the heat of and the catalytic action of the hot coke.

the vaporized and cracked products being removed through line 25 through a cyclone separator 25' serving to eliminate solid particles. The coke may be returned to reactor l2 through line 26 or fed through line 2l to a gas feed line 28 for return to reactor Ii. The gas or gas mixture fed through line 28 to react with and fluidize the coke in reactor il is dependent upon the type of product gas desired from reactor il. If synthesis gas, consisting essentially of carbon monoxide and hydrogen, be desired, the feed gas will contain relatively pure oxygen and steam. Tail gas from a synthesizing operation containing carbon dioxide, methane and hydrogen may also be used. It is to be understood that the qualities and the quantities of the gases fed through line 28 are not critical as respects the present invention and that they may be Varied widely, depending on the product gas desired.

The coke charged through line 28 is fluidized in reactor Il and a. part thereof gasied by exothermic reaction with the charged gases, the mass attaining a temperature of about 2000 F. The product gases are passed through a line 29, through a cyclone separator 39 and through line 3| to storage or use facilities such as a synthesis reactor, the hot coke being discharged through line It and returned to line I to begin the cycle anew.

From the foregoing, it is evident that the hydrocarbon oil or the products therefrom, except solid carbonaceous products, is not called upon to supply any of the heat requirements for the process. Substantially all the heat requirements are derived from the controlled exothermic reaction of the coke in reactor ll, that step being productive of a useful product in the form of the resulting gas mixture. Thus, the entire process is maintained on a high economic level.

Obviously, many modifications and variations of the invention as above set forth may be made without departing from the spirit and scope thereof and only such limitations should be imposed as are indicated in the appended claims.

I claim:

1. The process of treating a hydrocarbon oil and a solid carbonaceous material containing volatilizable constituents and a solid carbonaceous residue to produce valuable products, which comprises continuously circulating solid residue from said carbonaceous material through three intercommunicating zones, subjecting said solid residue in a gasication zone to an exothermc gasication reaction with a gaseous reactant, passing resulting heated solid residue from said gasification zone to a carbonization zone into admixture with fresh carbonaceous material thereby eifecting volatilization of volatilizable constituents from said material and formation of an additional amount of said solid residue, introducing said solid residue into a cracking zone into contact with said hydrocarbon oil thereby effecting cracking of said hydrocarbon oil with the resulting deposition of free carbon on said residue, and returning said solid residue from said cracking zone to said gasification zone wherein said carbon from said hydrocarbon oil and a portion of said solid residue. is gasied.

2. A process as defined in claim 1 wherein said gaseous reactant is an oxygen-containing gas.

3. The process of treating a hydrocarbon oil and a solid carbonaceous material containing volatilizable constituents and a solid carbonaceous residue to produce valuable products, which comprise introducing said solid material in comminuted form into admixture with a uidized mass of hot solid carbonaceous residue in a carbonization zone at a temperature suicient to effect volatilization of volatilizable constituents therefrom and produce additional fresh solid carbonaceous residue, passing the resulting mixture of solid residue from said carbonization zone to a cracking zone and bringing into contact therewith said hydrocarbon oil while effecting fluidization of a solid residue and cracking of said oil with the resulting deposition of free carbon on said residue, passing said free carbon and said solid residue from said cracking zone to a gasification zone into contact with an oxygencontaining gas effecting fluidization and exothermic gasification of said carbon from said hydrocarbon and a portion of the solid residue thereby raising the temperature of the ungasified portion of said solid residue to a temperature above that prevailing in said carbonization zone, passing said solid residue from said gasication zone to said carbonization zone, and separately recovering gaseous products from each of said zones.

4. The process defined in claim 3 wherein said carbonaceous material is coal and wherein thetemperature in the gasiiication zone is of the order of 2000* F., the temperature in the carbonization zone is in the range of about 1400 .to 1600 F., and the temperature in the cracking zone is in the range of about 900 to 1200D F.

5. The process defined in claim 4 wherein said oxygen-containing gas is a mixture of substantially pure oxygen and steam.

EARL W. RIBLETT.

REFERENCES CITED The following references are of record in the ile of this patent:

UNITED STATES PATENTS Number Name Date 1,899,887 Thiele Feb. 28, 1933 1,984,380 Odell Dec. 18, 1934 2,339,932 Kuhl Jan. 25, 1944 2,405,395 Bahlke et al Aug. 6, 1946 2,436,938 Scharmann Mar. 2, 1948 2,445,328 Keith July 20, 1948 FOREIGN PATENTS Number Country Date 578,711 Great Britain July 9, 1946 

1. THE PROCESS OF TREATING A HYDROCARBON OIL AND A SOLID CARBONACEOUS MATERIAL CONTAINING VOLATILIZABLE CONSTITUENTS AND A SOLID CARBONACEOUS RESIDUE TO PRODUCE VALUABLE PRODUCTS, WHICH COMPRISES CONTINUOUSLY CIRCULATING SOLID RESIDUE FROM SAID CARBONAEOUS MATERIAL THROUGH THREE INTERCOMMUNICATING ZONES, SUBJECTING SAID SOLID RESIDUE IN A GASIFICATION ZONE TO AN EXOTHERMIC GASIFICATION REACTION WITH A GASEOUS REACTANT, PASSING RESULTING HEATED SOLID RESIDUE FROM SAID GASIFICATION ZONE TO A CARBONIZATION ZONE INTO ADMIXTURE WITH FRESH CARBONACEOUS MATERIAL 